Method of making a sintered zinc battery anode structure



y 1968 Q I F. J. KELLY ETAL 3,384,482

METHOD OF MAKING A SINTERED ZINC BATTERY ANODE STRUCTURE Filed April 27, 1967 5 4 Sheets-Sheet 1 FIG. 2

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FRANCIS JOH/V KELLY FRA/VC/SZEK PRZYBYLA B): 6auanagA florman May 21, 1968 METHOD OF MAKING A SINTERED ZINC BATTERY ANODE STRUCTURE Filed April 27, 1967 POROS/TY 0F .Sl/VTERE'O ZINC STRUCTURES I96) F. .1. KELLY ETAL 3,384,482

4 Sheets-Sheet, 2

-3 OPT/MAL COMPACT/N6 PRESSURE X 10 (psi) [0 l2 l4 l6 l8 l'llll FILLING AGE/VT CONTENT) FIG. 4

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FRA/VC/S JOHN KELLY FRANC/SZEK PRZYBYLA Cauana A 7 flarman. 9

May 21, 1968 F. J. KELLY ETAL 3,384,482

METHOD OF MAKING A SINTERED ZINC BATTERY ANODE STRUCTURE Filed April 27, 1967 POROS/TY 0F ZINC STRUCTURE (96/ CELL TERMINAL VOLTAGE 4 Sheets-Sheet 3 EXPERIMENTAL PLANT CELL TIME {HOURS} F/G.5

com/warms PRESSURE x /0 (psi) FIG. 5

FRANCIS JOHN KELLY FRANC/SZEK PRZYBYLA BY: Caz/ana a Worman y 1, 1968 F. J. KELLY ETAL 3,384,482

METHOD OF MAKING A SINTERED ZINC BATTERY ANODE STRUCTURE 4 Sheets-Sheet 4 Filed April 27, 1967 EXPERIMENTAL PLANT CELL 6 7 8 9 101/ [2/3/4/5/6 TIME (HOURS) FIG. 7

n a A m um W L v1 mu 8 In m -w M, c 2 m5 M L z W m km 6 0 6 m -3 MM m L RR R m mFF w M. .0 w a m 5. I n w 5 TA 0 NC MU MM M '0 5 a m 1 0 z a z 0 0 0 United States Patent 3,384,482 METHOD 0F MAKING A SINTEREB ZINC BATTERY ANODE STRUCTURE Francis John Kelly, Toronto, Gntario, and Francrszek Przybyla, Port Credit, Ontario, Canada, assignors to Mallory Battery Company of Canada Limited, Sheridan Park, Ontario, (Ianada Filed Apr. 27, 1967, Ser. No. 634,227 Claims priority, applicgation Canada, May 20, 1966,

6 Claims. a. 75-201 ABSTRACT OF THE DISCLOSURE This invention relates to a sintered porous zinc structure and to the method of making same.

There is a need for metal structures of high porosity i.e. high surface area volume ratio and of sound structural integrity for application in electrode structures for electrical batteries and the like. Formerly useful electrode materials such as zinc and cadmium could not be formed into porous bodies by sintering. It is known that an oxide film on copper or on silver can be removed by hydrogen reduction at less than the melting point of copper or silver. The sintering of copper or silver powders to form relatively dense porous structures is not difficult. However oxide films on zinc and cadmium are not removed by hydrogen reduction at a temperature below the melting point of such metals. It is for this reason that to date there are no commercially known techniques for the production sintering of zinc and cadmium metal powders.

The formation of sintered porous metal structures by the utilization of carbon or hydrocarbon fillers adapted to determine the porosity of the structure and to be burnt out during sintering is known. However the employment of hydrocarbon filler materials for such purpose will tend to contaminate the resulting structure with residue. Not all of the products of combustion can be removed in this manner. Furthermore the combustion disrupts the structure during sintering or prior to sintering as the temperature is raised. Thus for example it is known that a mixture of carbon particles and iron oxide particles compacted and subjected to heat may swell and burst in the formation of sponge iron. Filler material combustion is an old technique and is subject to many limitations and in particular limitations as to the degree of porosity which may be achieved. Porosity in such prior structures is limited generally to substantially less than fifty percent and is controlled mainly by compacting pressures.

It is a main object of this invention to provide a porous metal structure and rnethod of making same in which the porosity is substantially independent of compacting pres- 3,384,482 Patented May 21, 196B ice sure relative to the structural integrity of the structure itself.

It is a further object of the invention to provide a porone metal structure of full structural integrity by vacuum sublimation of a sublimable filler mixed with a powdered metal to determine the porosity thereof and adapted to be removed completely by sublimation at a temperature near to and less than sintering temperature.

Other objects of the invention will be apparent from the following specification taken in conjunction with the accompanying drawings.

In the drawings:

FIGURE 1 is a photograph of a section of a porous metal structure according to Example 1 hereinafter.

FIGURE 2 is a photograph similar to that of FIGURE 1 for Example 3 hereinafter.

FIGURE 3 is a similar photograph of the structure resulting from Example 4 herein.

FIGURE 4 is a curve disclosing porosity as a function of filling agent content according to the invention.

FIGURE 5 is a set of curves disclosing the porosity of a porous structure herein as a function of compacting pressure.

FIGURE 6 records the life by a voltage time curve of a zinc structure herein used as a battery anode compared with a conventional battery anode at low temperature.

FIGURE 7 is a similar voltage time curve to that of FIGURE 6 for a different style of battery structure but again indicating the superiority of a cell employing the anode of the invention.

FIGURE 8 compares the cyclic discharge life of two battery cells one of which is conventional and the other of which embodies an anode formed of a zinc structure of the invention.

Zinc particles once exposed to air are coated with a thin superficial layer of oxide. In order to bond the particles at temperatures below the melting point by sintering it is mandatory that the oxide layer be removed. This layer however cannot be reduced by hydrogen at temperatures below the melting point of the rnetal.

It is therefore necessary to remove the oxide by a reaction other than reduction. According to the invention successful chemical reactions appear to be of the form:

in which X represents a chloride bromide or iodide ion. This reaction proceeds at a temperature considerably lower than the melting point of zinc. According to the invention the reaction product as well as any unchanged ammonium halide can be removed by sublimation under reduced pressure at such reaction temperature. At this and slightly higher temperatures the cleansed metal particle surfaces adhere in a preliminary sintering thus maintaining the particle structure established during the compacting process. Finally still under vacuum the zinc particle bonding is reinforced at the sintering temperature.

An essential feature of this method is that a preliminary bonding must be made between adjoining zinc particles concurrently with removal of the filling agent. This requires a sublimation temperature herein near the temperature at which sintering commences. This has been established as approximately C. below sintering temperature. At this temperature the ammonium halides sublime slowly enough for a mixed pellet to maintain its integrity.

Deformation of individual zinc particles begins to occur beyond 320 C. the maximum recommended temperature at which sintered zinc structures with predetermined size and shape can be obtained.

Only a very small quantity of ammonium halide is required to remove a zinc oxide film. The vast excess used in this process serves merely as filling agent. Ammonium halides are especially suitable as filling agents since they can be removed by vacuum sublimation at temperatures at which presintering of zinc simultaneously occurs. Thus the structural form achieved by compaction is preserved during the removal of the filling agent.

In order to achieve metal structures of a desired porosity and shape an intimate mixture of metal and filler particles is compressed. The shape is determined by the die and the ultimate porosity by the volume of metal to filler as shown in Table 1:

TABLE 1 Filling agent (lcrecnt content nu/w.)

NlhOl Nllmr Nlltl Poros ty of sintered vine pellet:

50% 18 19 130% 10 32 33 0500 24 37. 5 38. 5 70%" 30 43.5 44.5 757 3G. 5 50 51 80% a 45 57 58 81' a 48 60 61. 5

*Compaeting pressures listed in Table 2.

As shown in Table l and FIGURE 4 regulation of the filling agent content provides a very sensitive means of producing any desired porosity. As a consequence of their differing densities markedly different weight percentages of the various halides excepting fluorides are used in producing any one specified porosity.

The influence of compacting pressure on porosity is minor as can be seen from the pressure porosity graph of FIGURE 5. A twofold increase in compacting pressure (from 9,000 to 19,000 p.s.i.) reduces the porosity obtained by only 2%.

It is therefore necessary according to this invention to regulate the porosity by filling agent content rather than by compacting pressure. An optimal pressure can be chosen to yield pellets of suitable green strength. Experimentally determined optimal pressures are listed in Table 2.

TABLE 2 Filling agent content, Compacting pressure percent: (p.s.i.)

Example 1 An intimate mixture consisting of 6.00 g. of zinc powder (325 mesh, 3%; +325, 7%; +200, 30%; +100, 30%; +60, 30%; +20, 0%) and 2.51 g. of ammonium chloride (60 mesh, 100%) was compressed at 19,000 p.s.i. into a pellet. diameter 2.55 cm., height 0.53 cm. The pellet was placed in an evacuated (2 mm. Hg) glass sublimation apparatus and the temperature was raised quickly to 220 C. Ammonium chloride was sublimed quantitatively in the temperature range 220-240 C. The temperature was raised slowly to 280 C. and held at this temperature for approximately fifteen minutes. The apparatus still under evacuation was allowed to cool to room temperature and the pellet removed. The pellet resulting had a porosity of 69.5% (as measured by the volumetric method) and dimensions 2.54 cm. diameter 0.52 cm. height. The loss of zinc during the entire operation amounted to 2%. An enlarged (25X) photograph of the pellet structure is shown as FIGURE 1.

Example 2 The same mixture was compressed identically and the filling agent sublimed in the same way as in Example 1. The temperature was then raised from 240 C. to 320 C. and the apparatus immediately allowed to cool. The pellet resulting was identical with that obtained in Example 1.

Example 3 An intimate mixture consisting of 6.00 g. zinc powder (325 mesh, 3%; +325, 7%; +200, 30%; +100, 30%; +60, 30%; +20, 0%) and 4.1 g. ammonium bromide (60 mesh, was compressed at 14,000 p.s.i. into a pellet diameter 3.00 cm. height 0.38 cm. The pellet was placed in an evacuated (2 mm. Hg) sublimation apparatus and the temperature raised to 220 C. Ammonium bromide was sublimed quantitatively in the temperature range 220240 C. The temperature was raised slowly to 300 C. and held at this temperature for about ten minutes. The apparatus still under evacuation was allowed to cool to room temperature and the pellet was removed. The resulting pellet had a porosity of 68% and dimensions 2.99 cm. diameter and 0.37 cm. height. The loss of zinc during the entire operation amounted to 2%. An enlarged (25x) photograph of the pellet structure is shown as FIGURE 2.

Example 4 An intimate mixture of 6.00 g. zine powder (sieve analysis as in Example 3) and 2.45 g. ammonium iodide (-60 mesh, 100%) was compressed at a pressure of 12,000 p.s.i. into a pellet, diameter 3.00 cm. height 0.29 cm. The pellet was placed in an evacuated (2 mm. Hg) sublimation apparatus and the temperature raised to 200 C. Ammonium iodide was sublimed quantitatively in the temperature range 220-260 C. The temperature was raised slowly to 300 C. and held at this temperature for about ten minutes. The apparatus still under vacuum was allowed to cool to room temperature and the pellet removed. The resulting pellet had a porosity of 58%. The loss of Zinc during the entire operation amounted to 2%. An enlarged (25X) photograph of the pellet structure is shown as FIGURE 3.

From the foregoing it will be apparent that the sintered porous metal structure of the invention is of entire structural integrity i.e. each and every particle is bonded to at least one adjacent particle to define an open threedimensional network having communicating voids extending between the particles through the structure. In practice while the metal halide formed on the surface of the metal particles may be evaporated completely i.e. by controlled temperatures over a period of hours it is to be observed that such metal halides are soluble salts entirely compatible in small amounts with the chemistry of electrical applications as anodes of various kinds. The time of sintering sufiicient to impart a desired degree of structural integrity will leave trace amounts of soluble salts within the structure. A structure of the invention may thus be identified if made of substantially uniform sized irregularly shaped particles by a photographic appearance in section similar to that demonstrated by FIGURES 1, 2 and 3 and will ordinarily contain a trace amount of a soluble filler material or metal salt. Having regard to the unavailability of porous metal structures of entire structural integrity of zinc heretofore the existence of a porous structure of such metals containing at least a trace amount of a soluble salt will indicate this invention as its source.

Ammonium halides act as very efiicient reagents for Zinc oxide removal through solid state/vapor reactions under vacuum. Ammonium halides also serve as filling agents supporting zinc particles until they become bonded together by sintering into a porous structure. It has been discovered according to this invention that the functions of fiuxing agent and filling agent need not necessarily be combined in one substance. Experiments have shown that the overall time of sublimation and sintering can be decreased by using mixtures of benzoic acid and ammonium halides. This procedure also results in mechanically stronger porous structures. When using two-component mixtures the advantages conferred by benzoic acid appear to arise from the greater ease with which it can be sublimed. Nevertheless a minimum quantity of ammonium halide must be employed in order to obtain satisfactory cleansing of the zinc surfaces. This minimum quantity has been found to lie between -20% of the total weight of the filling mixture.

It was found impossible to sinter zinc powder using only benzoic acid. It may reasonably be inferred that benzoic acid functions mainly as a filling agent, while the ammonium halide functions mainly as a reagent for reactive sintering.

The invention also concerns methods of forming metal structures of entire structural integrity from particles of zinc which particles are not ordinarily adapted to be sintered due to the nature of the oxide film or coating formed thereon and present in normal atmosphere. A body may be formed according to this invention of a predetermined porosity determined by the volume of filler material employed for compaction with the metal particles. The filler is a mixture of soluble crystalline ammonium bromide chloride or iodide as a surface cleaner in cluding benzoic acid therewith. The filler employed must be characterized by a sublimation temperature not greater than the temperature at which sintering of the metal particles is to be achieved. The invention embodies the increasing of the rate of sublimation by pressure control to a pressure less than atmospheric. In the vacuum sublimation technique or reactive sintering as practised herein the filler materials will sublime at less than sintering temperature of the metal and at not less than about 180 C. below such sintering temperature. If the filler sublimes at too low a temperature i.e. at too great a temperature separation below the melting point of the metal i.e. below sintering temperature the structure will not be sufficiently supported during sintering. Preferably therefore the filler material should not sublime or the metal halides formed therefrom vaporize or distill at less than about 200 C. below the satisfactory sintering temperature at which sufiicient welding takes place. The sintering temperature may be somewhat less than melting temperature especially where a fresh metal surface is provided such as by the method and technique of the invention. Thus in some cases the sublimation temperature of the filler may be substantially below the melting temperature and yet deliver a porous body of high structural integrity according to the invention.

Porous metal structures of the invention demonstrate a very large active surface area. In FIGURE 6 an anode was set up in an experimental cell the anode being formed of zinc particles reactively sintered according to the invention with a filler of 20% ammonium chloride benzoic acid mixture. The experimental cell and the conventional plant type cell with which it was compared were identical in all other respects and were discharged at a current drain of 5 milliamperes at 1.25 volts at a temperature of 20 C. The conventional plant cell exhausted its practical life in less than three hours whereas the experimental cell maintained its practical life for substantially five times this useful life.

In FIGURE 7 a further comparison test with a similar type anode material but different type of cell structure was compared with a conventional plant cell identical in all other respects at a continuous discharge rate of 5 milliamperes at 1.3 volts at a temperature of 20 C. The useful life of the plant cell expired in less than 1 /2 hours whereas the experimental cell having an anode of the invention continued its useful life for more than 11 hours.

In FIGURE 8 is demonstrated an application of a zinc porous structure to an anode of an experimental cell compared with a conventional plant cell identical in all other respects at a temperature of 21 C. and a load of 14.5 ohms. This was an intermittent cyclic discharge of a program of 15 seconds on (to 0.8 volt) 45 seconds off. The useful cyclic discharge life of the anode of the invention again demonstrates its superiority in providing substantially four times the cyclic life of the conventional cell.

Vacuum reactive sintering of zinc of this invention involves the sublimation of the filler material at a rate which is accelerated by the use of vacuum. The fillers of the invention will sublime very slowly at normal temperature and pressure. A reduction of pressure combined with an increase in temperature greatly accelerates this property of the filler mixture crystals. While most of the filler is sublimed, that next the surface of the zinc particles enters into chemical reaction with the oxide layer on the surface of the particles to provide zinc complexes, which at higher temperatures decompose into ammonia and zinc halide.

Such metal salts are characterized by a predetermined vapour pressure at the melting temperature of the salt. The reduction of pressures accelerates the vaporization process and renders such mechanism practical.

While zinc bromide chloride and iodide vaporize at a temperature less than the melting temperature of zinc metal and are thus particularly suitable to the invention mechanism, it is to be noted that zinc fluoride formed by oxide reaction with a readily sublimable ammonium fluoride has a melting temperature much higher than the melting temperature of zinc. Accordingly while all halides are workable, the fluoride metal salt will remain in the structure as a substitute for oxide film and will be present in substantial quantity. In many applications this may not be a disadvantage since the structure will nevertheless be porous due to sublimation of the major portion of the filler and more than a trace amount of water soluble metal salt may be dissolved out of the structure if desired.

While the invention may find a variety of uses it is evident that battery cells having structurally superior anodes may be fabricated to provide many times the useful battery life of that experienced with battery cells of the prior art by this invention.

It is intended that the disclosures herein set forth should not be construed in any limiting sense other than that indicated by the scope of the following claims having regard to the art of forming sintered porous bodies of Zll'lC.

What is claimed is:

1. The method of sintering particles of zinc having an oxide coating thereon to form a body of entire structural integrity .of predetermined porosity and comprising: compacting said particles with a filler mixture of sublimable ammonium halide filler particles and benzoic acid at a sufiicient compacting pressure to provide a predetermined shape of suitable green strength; controlling the amount of filler particles to a volume substantially equal to said predetermined porosity; heating said compacted body to a sintering temperature less than the melting temperature .of zinc; during heating controlling the pressure of said body to a predetermined pressure less than atmospheric pressure adapted to accelerate and effect substantially complete sublimation of said filler from said body and maintaining structural support of said particles during heating up to substantially the temperature at which surfaces of said particles are joined by sintering.

2. A method according to claim 1 in which the filler comprises water soluble crystalline ammonium halide and benzoic acid.

3. The method according to claim 1 in which the oxide coating on said metal particles is replaced by a halide coating of said metal and said halide coating is vaporized at temperatures less than substantially sintering temperature to provide a fresh metal surface for said particles 7 conducive to the joining of the metals of said particles at sintering temperature.

4. The method according to claim 1 in which the filler comprises a mixture of benzoic acid and an ammonium halide in a ratio by weight of about 4:1.

5. The method according to claim 1 in which the body of predetermined shape formed at a compacting pressure is maintained at a temperature greater than about 200 C. below sintering temperature while under vacuum to provide vacuum sublimation of halide therein and after substantial sublimation of said halide the temperature is raised to sintering temperature.

6. The method according to claim 5 and the step Of UNITED STATES PATENTS 2,122,053 6/1938 Burkhardt 75222 2,129,844 9/1938 Kiefer 75-222 2,744,011 5/1956 Samuel 75-222 X CARL D. QUARFORTH, Primary Examiner.

A. J. STEINER, Assistant Exan'liner. 

